WO2018012453A1 - Gravure ink for lamination, printed material, and laminate - Google Patents

Abstract

The present invention provides a gravure ink for lamination, which exhibits good transferability to a base and good trapping properties during gravure printing, and which has a good appearance after lamination. A gravure ink for lamination according to the present invention contains (A) an organic pigment, (B) a binder resin, (C) silica particles and (D) an organic solvent, and satisfies the requirements (1) and (2) described below. (1) The gravure ink for lamination contains 0.1-3% by mass of the silica particles (C) in 100% by mass of the ink. (2) The gravure ink for lamination contains 0.1-20% by mass of (d1) a glycol ether organic solvent in 100% by mass of the organic solvent (D).

Description

Gravure ink for laminate, printed matter, and laminate

The present invention relates to a gravure ink for laminating, its printed matter, and a laminate.

When a film substrate such as an OPP film, PET film, or NY film is used as a packaging material or the like, printing using printing ink is usually performed for decoration or surface protection of the substrate. The printed substrate is subjected to a slitting process and a laminating process as necessary, and finally becomes a package for various uses such as food packaging and cosmetic packaging.

A gravure printing method may be mentioned as a printing method on the film substrate or paper substrate. In the plate used for the gravure printing method, the printed portions such as characters and patterns are concave portions (cells). The ink (gravure ink) is attached to the plate to the extent that the ink enters this recess (cell), and the ink is transferred to the base material by scraping off the excess ink on the surface using a doctor blade while the plate is rotated. Make it flesh. This printing method is suitable for reproduction of rich gradations such as photographs because it can express fine shades and is suitable for mass production because high-speed printing is possible.

In the laminating step, a film is further bonded onto the substrate on which the ink has been printed using an adhesive. The methods are roughly classified into three types: an extrusion laminating method, a dry laminating method, and a non-solvent laminating method.

JP-A-9-328646 JP 2013-144732 A JP 2010-270216 A JP 2005-298618 A JP 2013-213109 A

As problems of printability of the gravure printing method, there are (I) printing transfer failure and (II) trapping failure. (I) Print transfer failure refers to transfer failure of the ink to the substrate, and a distorted shape appears on the printed surface. This defect is also referred to as a plate or phenomenon, and is particularly likely to occur at a portion where the plate depth is shallow, that is, a portion where the cell depth is shallow (highlight portion). (II) The trapping failure is a printing failure in overprinting and is caused by insufficient wetting and spreading of the overlapping ink. Such print defects are handled as defective lots by the print converter, causing production loss.

Conventionally, various attempts have been made to improve printability. For example, a solvent-based gravure ink containing glycol ether or water has been proposed in order to improve the plate, that is, the properties (Patent Document 1). In order to improve the trapping property, a gravure ink using a single alcohol solvent as an organic solvent has been proposed (Patent Document 2). However, it is very difficult to satisfy all printability in gravure printing only by changing the type of organic solvent. Although it is conceivable to improve printability by changing the design of the binder resin used, a suitable design has not yet been established.

If there is a defective part in the printed matter, the possibility of causing a defect in the subsequent laminating process increases. Concerns about the laminating process include poor appearance, insufficient laminate strength, and insufficient boil resistance and retort resistance. Various attempts have been made to reduce these defects (Patent Documents 3 to 5). However, nothing has satisfied printability and laminate properties.

An object of the present invention is to provide a gravure ink for laminating which has good substrate transferability and trapping property in gravure printing, and has a good appearance after lamination.

As a result of intensive studies on the above problems, the present inventor has found that the above problems can be solved by using the printing ink for laminating described below, and has completed the present invention.

The gravure ink for laminating of the present invention is a gravure ink for laminating comprising an organic pigment (A), a binder resin (B), silica particles (C), and an organic solvent (D), and the following (1), (2 ).
(1) The silica particles (C) are contained in an amount of 0.1 to 3% by mass in 100% by mass of the ink.
(2) 0.1 to 20% by mass of the glycol ether organic solvent (d1) is contained in 100% by mass of the organic solvent (D).

The average particle diameter of the silica particles (C) is preferably 1 to 5 μm.
The surface tension of the glycol ether organic solvent (d1) is preferably 22.0 to 30.0 mN / m.

In one embodiment, the binder resin (B) can include a polyurethane resin (b1).

In the above aspect,
Binder resin (B)
Polyurethane resin (b1);
And at least one resin selected from the group consisting of vinyl chloride-vinyl acetate copolymer resin (b2), vinyl chloride-acrylic copolymer resin (b3) and cellulose resin (b4),
The total amount of the resins (b1) to (b4) is preferably 80 to 100% by mass in 100% by mass of the binder resin.

In the above embodiment, the binder resin (B) contains a polyurethane resin (b1) and a vinyl chloride-vinyl acetate copolymer resin (b2) in a total amount of 80 to 100% by mass in 100% by mass of the binder resin (B). The solid content mass ratio between (b1) and (b2) is preferably (b1) / (b2) = 95/5 to 40/60.

The printed matter of the present invention has a printed layer made of the printed matter of the gravure ink for laminating of the present invention on a substrate.

The laminated body of this invention has an adhesive layer and a film layer in order on the said printing layer of said printed matter of this invention.

According to the present invention, it is possible to provide a gravure ink for laminating that has good substrate transferability and trapping property in gravure printing and that has a good appearance after lamination.

Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention does not exceed the gist thereof. The content is not limited.

The gravure ink for laminating of the present invention is
The organic pigment (A), the binder resin (B), the silica particles (C), and the organic solvent (D) are included and satisfy the following (1) and (2).
(1) The silica particles (C) are contained in an amount of 0.1 to 3% by mass in 100% by mass of the ink.
(2) 0.1 to 20% by mass of the glycol ether organic solvent (d1) is contained in 100% by mass of the organic solvent (D).

<Organic pigment (A)>
In the present invention, the organic pigment (A) is used. Inks containing organic pigments are difficult to overprint in gravure printing, tend to have poor trapping properties, and are particularly difficult to overprint to superimpose different hues. However, in the gravure ink for laminating of the present invention, the trapping property is greatly improved by the combined use of the silica particles (C) and the glycol ether organic solvent (d1).
The organic pigment (A) is not particularly limited, but is soluble azo, insoluble azo, azo, phthalocyanine, halogenated phthalocyanine, anthraquinone, ansanthrone, dianthraquinonyl, anthrapyrimidine, perylene. , Perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethineazo, flavanthrone, diketopyrrolopyrrole, isoindoline, indanthrone, and carbon black pigments Is mentioned. For example, Carmine 6B, Lake Red C, Permanent Red 2B, Disazo Yellow, Pyrazolone Orange, Carmine FB, Chromophthal Yellow, Chromophthal Red, Phthalocyanine Blue, Phthalocyanine Green, Dioxazine Violet, Quinacridone Magenta, Quinacridone Red, Indanthrone Blue And pyrimidine yellow, thioindigo bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, and daylight fluorescent pigments.

The preferred specific examples of the organic pigment (A) are shown below with generic names of color indexes. The organic pigment preferably contains at least one selected from the group consisting of the following black pigments, indigo pigments, green pigments, red pigments, purple pigments, yellow pigments, orange pigments, and brown pigments. Furthermore, it is preferable to include at least one selected from the group consisting of black pigments, indigo pigments, red pigments, and yellow pigments. In particular, in the use of an indigo pigment and / or a red pigment, the printing effect (trapping property) of overprinting is improved, so that these uses are particularly preferable.

<Black pigment>
Specifically, C.I. I. Of the black pigments of CI Pigment Black 1 to 34, black pigments that are organic compounds or organometallic complexes are preferred. For example, C.I. I. Pigment black 1, C.I. I. Pigment black 6, C.I. I. Pigment black 7, C.I. I. Pigment black 9, and C.I. I. Pigment black 20 and the like.

<Indigo pigment>
Specifically, C.I. I. Of the cyan pigments of CI Pigment Blue 1 to 80, an indigo pigment which is an organic compound or an organometallic complex is preferable. For example, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 5, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 16, C.I. I. Pigment blue 17: 1, C.I. I. Pigment blue 22, C.I. I. Pigment blue 24: 1, C.I. I. Pigment blue 25, C.I. I. Pigment blue 26, C.I. I. Pigment blue 60, C.I. I. Pigment blue 61, C.I. I. Pigment blue 62, C.I. I. Pigment blue 63, C.I. I. Pigment blue 64, C.I. I. Pigment blue 75, C.I. I. Pigment blue 79, and C.I. I. And CI Pigment Blue 80.

<Green pigment>
Specifically, C.I. I. Of the green pigments of CI Pigment Green 1 to 50, green pigments that are organic compounds or organometallic complexes are preferred. For example, C.I. I. Pigment green 1, C.I. I. Pigment green 4, C.I. I. Pigment green 7, C.I. I. Pigment green 8, C.I. I. Pigment green 10 and C.I. I. And CI Pigment Green 36.

<Red pigment>
Specifically, C.I. I. Of the red pigments of CI Pigment Red 1 to 279, red pigments that are organic compounds or organometallic complexes are preferred. For example, C.I. I. Pigment Red 1 to C.I. I. Pigment red 12, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 17, C.I. I. Pigment red 18, C.I. I. Pigment red 19, C.I. I. Pigment red 20, C.I. I. Pigment red 21, C.I. I. Pigment red 22, C.I. I. Pigment red 23, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 38, C.I. I. Pigment red 41, C.I. I. Pigment red 43, C.I. I. Pigment red 46, C.I. I. Pigment red 48, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 48: 5, C.I. I. Pigment red 48: 6, C.I. I. Pigment red 49, C.I. I. Pigment red 49: 1, C.I. I. Pigment red 49: 2, C.I. I. Pigment red 49: 3, C.I. I. Pigment red 52, C.I. I. Pigment red 52: 1, C.I. I. Pigment red 52: 2, C.I. I. Pigment red 53, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 53: 2, C.I. I. Pigment red 53: 3, C.I. I. Pigment red 54, C.I. I. Pigment red 57, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 58, C.I. I. Pigment red 58: 1, C.I. I. Pigment red 58: 2, C.I. I. Pigment red 58: 3, C.I. I. Pigment red 58: 4, C.I. I. Pigment red 60: 1, C.I. I. Pigment red 63, C.I. I. Pigment red 63: 1, C.I. I. Pigment red 63: 2, C.I. I. Pigment red 63: 3, C.I. I. Pigment red 64: 1, C.I. I. Pigment red 68, C.I. I. Pigment red 68, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 83, C.I. I. Pigment red 88, C.I. I. Pigment red 89, C.I. I. Pigment red 95, C.I. I. Pigment red 112, C.I. I. Pigment red 114, C.I. I. Pigment red 119, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 136, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 147, C.I. I. Pigment red 149, C.I. I. Pigment red 150, C.I. I. Pigment red 164, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 169, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 172, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 181, C.I. I. Pigment red 182, C.I. I. Pigment red 183, C.I. I. Pigment red 184, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 188, C.I. I. Pigment red 190, C.I. I. Pigment red 192, C.I. I. Pigment red 193, C.I. I. Pigment red 194, C.I. I. Pigment red 200, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 208, C.I. I. Pigment red 209, C.I. I. Pigment red 210, C.I. I. Pigment red 211, C.I. I. Pigment red 213, C.I. I. Pigment red 214, C.I. I. Pigment red 216, C.I. I. Pigment red 215, C.I. I. Pigment red 216, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 223, C.I. I. Pigment red 224, C.I. I. Pigment red 226, C.I. I. Pigment red 237, C.I. I. Pigment red 238, C.I. I. Pigment red 239, C.I. I. Pigment red 240, C.I. I. Pigment red 242, C.I. I. Pigment red 245, C.I. I. Pigment red 247, C.I. I. Pigment red 248, C.I. I. Pigment red 251, C.I. I. Pigment red 253, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 256, C.I. I. Pigment red 257, C.I. I. Pigment red 258, C.I. I. Pigment red 260, C.I. I. Pigment red 262, C.I. I. Pigment red 263, C.I. I. Pigment red 264, C.I. I. Pigment red 266, C.I. I. Pigment red 268, C.I. I. Pigment red 269, C.I. I. Pigment red 270, C.I. I. Pigment red 271, C.I. I. Pigment red 272, and C.I. I. And CI Pigment Red 279.

<Purple pigment>
Specifically, C.I. I. Of the purple pigments of CI Pigment Violet 1 to 50, purple pigments that are organic compounds or organometallic complexes are preferred. For example, C.I. I. Pigment violet 1, C.I. I. Pigment violet 2, C.I. I. Pigment violet 3, C.I. I. Pigment violet 3: 1, C.I. I. Pigment violet 3: 3, C.I. I. Pigment violet 5: 1, C.I. I. Pigment violet 13, C.I. I. Pigment violet 19 (γ type, β type), C.I. I. Pigment violet 23, C.I. I. Pigment violet 25, C.I. I. Pigment violet 27, C.I. I. Pigment violet 29, C.I. I. Pigment violet 31, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 37, C.I. I. Pigment violet 38, C.I. I. Pigment violet 42, and C.I. I. And CI Pigment Violet 50.

<Yellow pigment>
Specifically, C.I. I. Of the yellow pigments of CI Pigment Yellow 1 to 219, yellow pigments that are organic compounds or organometallic complexes are preferred. For example, C.I. I. Pigment yellow 1, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, pigment yellow 17, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 42, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 65, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 86, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 117, C.I. I. Pigment yellow 120, pigment yellow 125, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 137, C.I. I. Pigment, yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 148, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 174, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185, and C.I. I. And CI Pigment Yellow 213.

<Orange pigment>
Specifically, C.I. I. Of the orange pigments of CI Pigment Orange 1 to 81, an orange pigment which is an organic compound or an organometallic complex is preferable. For example, C.I. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 16, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 37, C.I. I. Pigment o orange 38, C.I. I. Pigment orange 43, C.I. I. Pigment orange 51, C.I. I. Pigment range 55, C.I. I. Pigment orange 59, C.I. I. Pigment orange 61, C.I. I. Pigment orange 64, C.I. I. Pigment orange 71, and C.I. I. And CI Pigment Orange 74.

<Brown pigment>
For example, C.I. I. Pigment brown 23, C.I. I. Pigment brown 25, and C.I. I. And CI Pigment Brown 26.

Among the above, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 146, C.I. I. Pigment red 242, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 14, C.I. I. Pigment orange 38, C.I. I. Pigment orange 13, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 139, C.I. I. Pigment cocoon red 185, C.I. I. Pigment red 122, C.I. I. Pigment red 178, C.I. I. Pigment red 149, C.I. I. Pigment red 144, C.I. I. Pigment cocoon red 166, C.I. I. Pigment violet 23, C.I. I. Pigment violet 37, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment green 7, C.I. I. Pigment orange 34, C.I. I. Pigment orange 64, and C.I. I. Pigment Black 7 and the like are preferable. It is preferable to use at least one organic pigment selected from these groups.

The organic pigment is an amount sufficient to make the density and coloring power of the gravure ink for lamination suitable, specifically, 1 to 50% by mass with respect to the total amount of ink, and 10 to 90% by mass in the solid content of the ink. % Is preferably included. A pigment can be used individually by 1 type or in combination of 2 or more types. In the present specification, “solid content” refers to the total nonvolatile components excluding liquids such as organic solvents and water.

The gravure ink for laminating of the present invention can be used for printing in combination with inks of other hues as required. Ink colors include five basic colors: yellow, red, indigo, black, and white; process gamut external colors are red (orange), grass (green), purple, transparent yellow, peony, vermilion, brown, and pearl Is mentioned.

<Binder resin (B)>
The binder resin (B) used in the present invention is not particularly limited. For example, acrylic resin, polyester resin, styrene resin, styrene-maleic acid resin, maleic acid resin, polyamide resin, polyurethane resin (b1), chloride Examples thereof include vinyl-vinyl acetate copolymer resin (b2), vinyl chloride-acrylic copolymer resin (b3), and cellulose resin (b4). Preferably, it is at least one selected from polyurethane resin (b1), vinyl chloride-vinyl acetate copolymer resin (b2), vinyl chloride-acrylic copolymer resin (b3), and cellulose resin (b4).
The binder resin (B) preferably includes a polyurethane resin (b1), more preferably a polyurethane resin (b1), a vinyl chloride-vinyl acetate copolymer resin (b2), and a vinyl chloride-acrylic copolymer resin (b3). And at least one resin selected from the group consisting of cellulosic resins (b4). The binder resin (B) preferably contains 80 to 100% by mass of the resins (b1) to (b4) in 100% by mass of the binder resin. More preferably, it is 90 to 100% by mass.

<Polyurethane resin (b1)>
The weight average molecular weight of the polyurethane resin (b1) is preferably 10,000 to 100,000, the glass transition temperature is preferably −60 to 40 ° C., and the storage elastic modulus at 40 ° C. in the dynamic viscoelasticity measurement. Is preferably 1 to 100 MPa. In addition, in this specification, a glass transition temperature is measured using a differential scanning calorimeter (DSC), and represents the middle point of the temperature range where a glass transition occurs.

The polyurethane resin (b1) preferably has an amine value and / or a hydroxyl value. The amine value is preferably 1.0 to 20.0 mgKOH / g. The hydroxyl value is preferably 1.0 to 20.0 mgKOH / g.

The polyurethane resin (b1) preferably contains a structural unit derived from polyether polyol, and the content thereof is preferably 5 to 80% by mass, more preferably 100% by mass of the solid content of the polyurethane resin (b1). 10 to 50% by mass.

The polyurethane resin (b1) preferably contains a structural unit derived from a polyester polyol, and the content thereof is preferably 5 to 80% by mass, more preferably 10% in 100% by mass of the solid content of the polyurethane resin (b1). It is ˜70% by mass, particularly preferably 30 to 70% by mass.

The polyurethane resin (b1) is not particularly limited and is appropriately produced by a known method. For example, a polyurethane resin obtained from a polyol and a polyisocyanate; a polyurethane resin obtained by reacting a urethane prepolymer of a terminal isocyanate obtained from a polyol and a polyisocyanate with an amine chain extender is preferable.

Examples of the polyol include polyester polyol, polyether polyol, polycaprolactone diol, polycarbonate polyol, polyolefin polyol, castor oil polyol, hydrogenated castor oil polyol, dimer diol, and hydrogenated dimer diol. Among these, polyether polyol and polyester polyol are preferable.

Examples of polyether polyols include polyether polyols that are (co) polymers such as ethylene oxide, propylene oxide, and tetrahydrofuran. Among these, polytetramethylene glycol, polypropylene glycol, and polyethylene glycol are preferable. The number average molecular weight is preferably 500 to 10,000. The number average molecular weight can be calculated from the hydroxyl value because the terminal is a hydroxyl group, and is obtained from (Equation 1).
(Formula 1) Number average molecular weight of polyol = 1000 × 56.1 × hydroxyl number of hydroxyl group / hydroxyl value

Examples of the polyester polyol include condensates obtained by an esterification reaction between a dibasic acid and a diol.
Dibasic acids include adipic acid, phthalic anhydride, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, pimelic acid, azelaic acid, sebacic acid, suberic acid, glutaric acid, 1 4-cyclohexyldicarboxylic acid, dimer acid, hydrogenated dimer acid, and the like.
Diols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, and 1,8-octanediol. 1,9-nonanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 3,3,5-trimethylpentanediol, 2,4-diethyl- 1,5-pentanediol, 1,12-octadecanediol, 1,2-alkanediol, 1,3-alkanediol, 1-monoglyceride, 2-monoglyceride, 1-monoglycerin ether, 2-monoglycerin ether, dimer diol , And hydrogenated dimer o Etc. The.
Polyester polyols can be used alone or in combination of two or more.

As the diol, a diol having a branched structure is preferable. The diol having a branched structure is a diol having an alkyl side chain in which at least one hydrogen atom of an alkylene group contained in the diol is substituted with an alkyl group. For example, propylene glycol, 1,3-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,4-pentanediol, 3-methyl-1,5-pentanediol, 2,5-hexane Diol, 2-methyl-1,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,8-octane Examples thereof include diol, 2,2,4-trimethyl-1,3-pentanediol, and 2,2,4-trimethyl-1,6-hexanediol. These are particularly preferable for improving printability, printing effect, and laminate strength.
As the dibasic acid, sebacic acid and / or adipic acid is particularly preferred. Also, a polyol having 3 or more hydroxy groups and / or a polyvalent carboxylic acid having 3 or more carboxy groups can be used in combination.

The number average molecular weight of the polyester polyol is preferably 500 to 10,000. The number average molecular weight is determined by the above (Formula 1). The acid value of the polyester polyol is preferably 1.0 mgKOH / g or less, and more preferably 0.5 mgKOH / g or less.

Known polyisocyanates can be used, and examples thereof include aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates.
Examples of aromatic diisocyanates include 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetra Alkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, bis-chloromethyl-diphenylmethane diisocyanate, xylylene diisocyanate, And 2,6-diisocyanate-benzyl chloride.
Examples of the aliphatic diisocyanate include butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate.
Examples of the alicyclic diisocyanate include cyclohexane-1,4-diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, dimeryl diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, Examples thereof include methylcyclohexane diisocyanate, norbornane diisocyanate, and dimerized isocyanate obtained by converting a carboxy group of dimer acid into an isocyanate group.
These may be trimers to form an isocyanurate ring structure. These polyisocyanates can be used alone or in combination of two or more.
Of these, aromatic diisocyanates and / or alicyclic diisocyanates are preferred. Among the polyisocyanates exemplified above, tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, isocyanurate of hexamethylene diisocyanate, and the like are preferable.

The amine chain extender is not particularly limited, and an amine chain extender having a molecular weight of 500 or less is preferable, and examples thereof include a diamine group and a trifunctional or higher polyfunctional amine group.
For example, diamine chain extenders such as ethylenediamine, propylenediamine, hexamethylenediamine, pentamethylenediamine, isophoronediamine, dicyclohexylmethane-4,4′-diamine, and p-phenylenediamine;
2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypyrroleethylenediamine Diamine-based chain extenders having a hydroxyl group such as di-2-hydroxypyrroleethylenediamine and di-2-hydroxypropylethylenediamine;
Diethylenetriamine, iminobispropylamine (IBPA, 3,3′-diaminodipropylamine), triethylenetetramine, N- (3-aminopropyl) butane-1,4-diamine (spermidine), 6,6-iminodihexylamine 3 or more polyfunctional amine chain extenders such as 3,7-diazanonan-1,9-diamine and N, N′-bis (3-aminopropyl) ethylenediamine;
These chain extenders can be used alone or in combination of two or more. Of these, isophoronediamine, hexamethylenediamine, iminobispropylamine, and the like are preferable.

If necessary, a monovalent active hydrogen compound can be used as a polymerization terminator for the purpose of terminating the excess reaction. Such a compound is not particularly limited as long as it is a monoamine compound having a primary or secondary amino group, and examples thereof include dialkylamines such as di-n-butylamine and aminoalcohols such as 2-ethanolamine. can give. Furthermore, amino acids such as glycine and L-alanine can be used as a polymerization terminator, particularly when it is desired to introduce a carboxy group into the polyurethane resin. When using a polymerization terminator, the chain terminator and chain extender may be used together to carry out the chain extension reaction, or after a certain amount of chain extension reaction with the chain extender, the polymerization terminator is added alone. Then, a polymerization termination reaction may be performed. On the other hand, the molecular weight can be controlled without using a polymerization terminator, but in this case, a method of adding a prepolymer to a solution containing a chain extender is preferable in terms of reaction control.

As a synthesis method of the polyurethane resin (b1), a polyol and a polyisocyanate are reacted to obtain a prepolymer having an isocyanate group at a terminal, and this prepolymer is reacted with an amine chain extender and, if necessary, a polymerization terminator. A prepolymer method for synthesizing the polyurethane resin (b1) is preferred. For example, a polyol and a polyisocyanate are reacted at a temperature of 50 to 150 ° C. using a solvent inert to an isocyanate group as necessary, and further using a urethanization catalyst as necessary (urethanization reaction), A prepolymer method is preferred in which a prepolymer having an isocyanate group at the terminal is obtained, and then this prepolymer is reacted with an amine chain extender and, if necessary, a polymerization terminator to obtain a polyurethane resin (b1).
Other synthesis methods include a so-called one-shot method in which a polymer polyol, polyisocyanate, an amine chain extender, and if necessary, a polymerization terminator are reacted in a single step to obtain a polyurethane resin (b1).

In producing the prepolymer, the amount of polyol and polyisocyanate is such that the NCO / OH ratio, which is the ratio of the number of moles of isocyanate groups in the polyisocyanate to the total number of moles of hydroxyl groups in the polyol, is 1.1 to 3. It is preferable to determine so as to be in the range of 0. More preferably, the NCO / OH ratio is 1.3 to 2.5.

From the viewpoint of reaction control, it is preferable to use an organic solvent for the synthesis of the prepolymer. As the organic solvent, an organic solvent inactive to the isocyanate group is preferable. For example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethers such as dioxane and tetrahydrofuran; aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; And halogen-based hydrocarbons. These can be used individually by 1 type or in combination of 2 or more types.

In the prepolymer synthesis reaction, a catalyst can be used as necessary. Examples of the catalyst include tertiary amine catalysts such as triethylamine and dimethylaniline; metal catalysts such as tin and zinc. These catalysts are usually used in the range of 0.001 to 1 mol% with respect to the polyol compound.

A prepolymer having an isocyanate group at the terminal and an amine chain extender such as diamine and / or triamine are reacted at 10 to 60 ° C. to obtain a high molecular weight polyurethane resin (b1) containing an active hydrogen group at the terminal. It is done.

The ratio of the total number of moles of amino groups of the amine chain extender to the number of moles of isocyanate groups in the prepolymer is 1.01 to 2.00, preferably 1.03 to 1.06. It is preferable to carry out.

<Vinyl chloride-vinyl acetate copolymer resin (b2)>
The vinyl chloride-vinyl acetate copolymer resin is a resin mainly composed of a copolymer of vinyl chloride and vinyl acetate. The weight average molecular weight is preferably 5,000 to 100,000, and more preferably 20,000 to 70,000. In 100% by mass of the solid content of the vinyl chloride-vinyl acetate copolymer resin (b2), the content of the structural unit derived from the vinyl acetate monomer is 1 to 30% by mass, and the content of the structural unit derived from the vinyl chloride monomer is 70 to 95. It is preferable that it is mass%. In this case, solubility in an organic solvent is improved, adhesion to a substrate, film properties, laminate strength, and the like are improved. In order to improve the solubility in an organic solvent, the vinyl chloride-vinyl acetate copolymer resin (b2) further preferably contains a hydroxyl group derived from vinyl alcohol introduced by a saponification reaction or copolymerization, and the hydroxyl value is 20 It is preferably ˜200 mg KOH / g. The glass transition temperature is preferably 50 to 90 ° C.

<Vinyl chloride-acrylic copolymer resin (b3)>
The vinyl chloride-acrylic copolymer resin (b3) is a resin mainly composed of a copolymer of a vinyl chloride monomer and an acrylic monomer. The acrylic monomer preferably contains (meth) acrylic acid hydroxyalkyl ester, because adhesion to the substrate and solubility in an organic solvent are improved. The acrylic monomer may be incorporated into the main chain of polyvinyl chloride in a block arrangement or a random arrangement, or may be grafted to the side chain of polyvinyl chloride. The vinyl chloride-acrylic copolymer resin (b3) preferably has a weight average molecular weight of 10,000 to 100,000, and more preferably 30,000 to 70,000.

The content of the structural unit derived from the vinyl chloride monomer in the vinyl chloride-acrylic copolymer resin (b3) is 70 to 95% by mass in 100% by mass of the vinyl chloride-acrylic copolymer resin (b3) solid content. It is preferable. In this case, solubility in an organic solvent is improved, and adhesion to a substrate, film properties, laminate strength, and the like are improved.

In this specification, “(meth) acryl” is a generic term for methacryl and acryl, and “(meth) acrylate” is a generic term for methacrylate and acrylate.

Examples of the acrylic monomer include (meth) acrylic acid alkyl ester, and the alkyl group preferably has 1 to 20 carbon atoms. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, and (meth) acryl And octadecyl acid. The alkyl group may further have a benzene ring structure. These can be used individually by 1 type or in combination of 2 or more types.

The acrylic monomer preferably has a hydroxyl group. Examples of the acrylic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, ( (Meth) acrylic acid hydroxyalkyl esters such as 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyoctyl (meth) acrylate; Glycol mono (meth) acrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and 1,4-cyclohexanedimethanol mono (meth) acrylate; caprolactone modified (meth) acrylate ; Hydroxyethyl acrylamide. These can be used individually by 1 type or in combination of 2 or more types. Of these, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxypropyl acrylate are more preferable because they improve solubility in solvents.

The acrylic ester may have a functional group other than a hydroxyl group. Examples of functional groups include a carboxy group, an amide bond group, an amino group, and an alkylene oxide group.

<Cellulose-based resin (b4)>
Examples of the cellulose resin (b4) include nitrocellulose, cellulose acetate propionate, cellulose acetate butyrate, hydroxyalkyl cellulose, and carboxyalkyl cellulose. Examples of the alkyl group optionally contained in the cellulose resin include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, and a hexyl group. The alkyl group may have a substituent. Among these, cellulose acetate propionate, cellulose acetate butyrate, and nitrocellulose are preferable. The weight average molecular weight is preferably 5,000 to 1,000,000, and more preferably 10,000 to 200,000. The glass transition temperature is preferably 120 to 180 ° C.

In the gravure ink for laminating of the present invention, the binder resin (B) preferably contains 80 to 100% by mass of the polyurethane resin (b1) and the vinyl chloride-vinyl acetate copolymer resin (b2) in total. The mass ratio ((b1) / (b2)) between the resin (b1) and the resin (b2) is preferably 95/5 to 40/60, more preferably 90/10 to 50/50. If it is this range, printability, base-material adhesiveness, coating-film physical property, and laminate strength will become favorable.

In 100% by mass of the gravure ink of the present invention, the binder resin (B) is preferably contained in a solid content of 3.0 to 25.0% by mass.

<Silica particles (C)>
The silica particles (C) may be natural products or synthetic products, may be crystalline or non-crystalline, and may be hydrophobic or hydrophilic. As a method for synthesizing silica particles, there are dry methods such as a combustion method and an arc method; wet methods such as a precipitation method and a gel method. It may be synthesized by any method. The silica particle (C) may be a hydrophilic silica particle having a hydrophilic functional group on the surface, or may be a hydrophobic silica particle obtained by modifying the hydrophilic functional group with alkylsilane or the like to make it hydrophobic. preferable. The ink containing hydrophilic silica particles promotes the wetting and spreading of the ink during overprinting, and has the effect of improving the overprinting effect (also referred to as trapping property). In 100% by mass of the gravure ink for lamination of the present invention, the content of the silica particles (C) is 0.1 to 3.0% by mass. The content is preferably 0.2 to 2.5% by mass, more preferably 0.2 to 1.5% by mass.

The silica particles (C) preferably have an average particle diameter of 1 to 5 μm in order to make appropriate irregularities on the surface of the ink layer. In addition, the average particle diameter of a silica particle means the particle size in the integrated value 50% (D50) in a particle size distribution, and can be calculated | required by the Coulter counter method.
The silica particles (C) preferably have a specific surface area measured by the BET method of 50 to 600 m ² / g. More preferably, it is 100 m to 450 m ² / g. A plurality of types of silica particles (C) having different average surface diameters and / or specific surface areas according to the BET method may be used in combination.

<Organic solvent (D)>
The gravure ink for lamination of the present invention contains an organic solvent (D) as a liquid medium. Examples of the organic solvent (D) include aromatic organic solvents (so-called toluene organic solvents) and non-aromatic organic solvents that do not contain an aromatic ring (so-called non-toluene organic solvents). Examples of the aromatic organic solvent include toluene and xylene. Non-aromatic organic solvents include, for example, ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester organic solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, and isobutyl acetate; methanol, ethanol, n-propanol Alcohol-based organic solvents such as isopropanol and n-butanol. These can be used individually by 1 type or in combination of 2 or more types. Among these, non-aromatic organic solvents that do not contain an aromatic ring (so-called non-toluene organic solvents) are preferable, and non-aromatic organic solvents other than ketone-based organic solvents such as methyl ethyl ketone (hereinafter referred to as “MEK”), Specifically, ester organic solvents and / or alcohol organic solvents are more preferable.
The gravure ink for laminating of the present invention may contain water as a liquid medium. The content thereof is preferably 0.1 to 10% by mass in 100% by mass of the liquid medium.

<Glycol ether organic solvent (d1)>
The gravure ink for lamination of the present invention contains 0.1 to 20% by mass of the glycol ether organic solvent (d1) in 100% by mass of the organic solvent (D). When the glycol ether organic solvent (d1) is contained in the above range and used in combination with the silica particles (C), a synergistic effect is exhibited, and the printing effect (trapping property) in the overprinting is drastically improved. This mechanism is not particularly limited, and the silica particles (C) create appropriate irregularities on the surface of the printing surface, improve the wetting spread of the ink printed thereon, and further the glycol ether organic solvent (d1 )) And wetting and spreading effects, and it is assumed that a synergistic effect is exhibited. The content of the glycol ether organic solvent (d1) is preferably 0.5 to 17% by mass, and more preferably 0.5 to 15% by mass.

Examples of the glycol ether organic solvent (d1) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol monoisopropyl ether, and ethylene glycol dipropyl. Ethylene such as ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol dibutyl ether, ethylene glycol isoamyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, methoxyethoxyethanol, and ethylene glycol monoallyl ether Glycol A Le acids;
Diethylene glycol ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol monohexyl ether, and diethylene glycol mono 2-ethylhexyl ether Kind;
Triethylene glycol ethers such as triethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, and triethylene glycol dimethyl ether;
Propylene glycol ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and butoxypropanol;
Dipropylene glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether;
And tripropylene glycol ethers such as tripropylene glycol monomethyl ether.
These can be used individually by 1 type or in combination of 2 or more types.

The glycol ether organic solvent (d1) may be esterified, and those obtained by acetate formation of the glycol monoether can be preferably used. Typical examples include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Etc.

The glycol ether organic solvent (d1) is preferably at least one organic solvent selected from the group consisting of ethylene glycol ethers, diethylene glycol ethers, propylene glycol ethers, and dipropylene glycol ethers.

The glycol ether organic solvent (d1) preferably has a surface tension of 22.0 to 30.0 mN / m in order to promote an improvement in trapping property due to a synergistic effect with the hydrophilic silica particles. Further, it is preferably water-soluble, and its boiling point is preferably 115 to 245 ° C. The glycol ether organic solvent (d1) is not particularly limited, and examples thereof include the following organic solvents.
Ethylene glycol monomethyl ether (surface tension 26.6 mN / m, boiling point 124.5 ° C.),
Diethylene glycol monomethyl ether (surface tension 29.8 mN / m, boiling point 194.0 ° C.),
Ethylene glycol mono-n-propyl ether (surface tension 23.3 mN / m, boiling point 151.0 ° C.),
Ethylene glycol monoisopropyl ether (surface tension 22.9 mN / m, boiling point 141.8 ° C.),
Diethylene glycol monoisopropyl ether (surface tension 29.9 mN / m, boiling point 207.0 ° C.),
Ethylene glycol monobutyl ether (surface tension 24.0 mN / m, boiling point 171.2 ° C.),
Diethylene glycol monobutyl ether (surface tension 26.2 mN / m, boiling point 230.6 ° C.),
Ethylene glycol monoisobutyl ether (surface tension 22.5 mN / m, boiling point 160.5 ° C.),
Propylene glycol monomethyl ether (surface tension 23.5 mN / m, boiling point 121.0 ° C.),
Dipropylene glycol monomethyl ether (surface tension 25.1 mN / m, boiling point 187.2 ° C.),
Propylene glycol mono n-propyl ether (surface tension 22.8 mN / m, boiling point 149.8 ° C.),
Diethylene glycol dimethyl ether (surface tension 25.2 mN / m, boiling point 162 ° C.),
Diethylene glycol methyl ethyl ether (surface tension 24.0 mN / m, boiling point 176.0 ° C.),
Diethylene glycol diethyl ether (surface tension 23.3 mN / m, boiling point 188.9 ° C.).

For measuring the surface tension of glycol ether organic solvent (d1), Wilhelmy method (also referred to as plate method or vertical plate method), du Nouy method (also referred to as ring method or ring method), hanging drop method (pendant A drop method), a maximum bubble pressure method, a method of measuring a contact angle and calculating from a Young's formula. Any method may be used, but a measurement method according to JIS K 2241 of the du Nouy method (ring method, ring method) is preferable.

<Other resins that can be used in combination>
The gravure ink for laminating of the present invention may contain other polymer material as necessary. Other polymer materials include, for example, chlorinated polypropylene resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, alkyd resins, polyvinyl chloride resins, rosin resins, rosin modified maleic resins, terpene resins, phenol modified Examples thereof include terpene resins, ketone resins, cyclized rubbers, chlorinated rubbers, butyrals, petroleum resins, and modified resins thereof. These resins can be used alone or in combination of two or more. The content is preferably 1 to 20% by mass in 100% by mass of the solid content of the binder resin (B).

<Additives>
The gravure ink for lamination of the present invention can contain one or more known additives as required. Known additives include, for example, pigment derivatives, dispersants, wetting agents, adhesion aids, leveling agents, antifoaming agents, antistatic agents, trapping agents, antiblocking agents, wax components, isocyanate curing agents, and silane cups. A ring agent etc. are mentioned.

For example, a dispersant can be used to stably disperse the pigment. As the dispersant, surfactants such as anionic, nonionic, cationic and amphoteric can be used. From the viewpoint of the storage stability of the ink, the content of the dispersant is preferably 0.1 to 10.0% by mass, and preferably 0.1 to 3.0% by mass with respect to 100% by mass of the total amount of the ink. It is more preferable that

<Manufacture of ink>
The gravure ink for lamination of the present invention can be produced by dissolving and / or dispersing the organic pigment (A), the binder resin (B), and the silica particles (C) in the organic solvent (D). For example, an organic pigment (A), silica particles (C), a polyurethane resin (b1), a vinyl chloride-vinyl acetate copolymer resin (b2) and, if necessary, a dispersant are mixed, and these are mixed into an organic solvent (D). The resulting pigment dispersion is further blended with a polyurethane resin (b1), a glycol ether solvent (d1), and, if necessary, other resins and / or additives. Thus, a gravure ink for laminating can be produced.
In addition, a dispersion of silica particles (C) with an organic solvent (D) and a binder resin (B) is manufactured in advance, and the ink manufactured at the time of ink manufacture or without silica particles (C) is used. You may add and use.

The particle size distribution of the pigment dispersion is adjusted by appropriately adjusting the size of the grinding media of the disperser, the filling rate of the grinding media, the dispersion treatment time, the discharge speed of the pigment dispersion, the viscosity of the pigment dispersion, and the like. Can do. As the disperser, known dispersers such as a roller mill, a ball mill, a pebble mill, an attritor, and a sand mill can be used.
When air bubbles and unexpected coarse particles are contained in the ink, it is preferably removed by filtration or the like in order to reduce the quality of the printed matter. A conventionally well-known filter can be used.

The viscosity of the gravure ink for laminating produced by the above method is in the range of 40 to 400 cps at 25 ° C. with a B-type viscometer in order to correspond to high speed printing (50 to 300 m / min) by the gravure printing method. Preferably there is. More preferably, it is 50 to 350 cps. This viscosity range corresponds to a viscosity of 9 to 40 seconds in Zahn cup # 4. The viscosity of the gravure ink is adjusted by appropriately selecting the type and / or amount of raw materials used, for example, the amount of organic pigment (A), binder resin (B), organic solvent (D) and the like. Can do. The viscosity of the ink can also be adjusted by adjusting the particle size and particle size distribution of the organic pigment in the ink.

<Printed matter>
The gravure ink of the present invention can be printed by a gravure printing method. The gravure ink of the present invention can be diluted, for example, to a viscosity and concentration suitable for gravure printing using a diluting solvent as needed, and can be supplied to a printing unit alone or in combination of two or more. . Printing is performed on the substrate using the gravure ink of the present invention, and a volatile component is removed by drying to form a printed layer, whereby a printed matter can be obtained. In addition, you may add the dispersion | distribution by the organic solvent (D) of a silica particle (C) and binder resin (B) later for adjustment of trapping property at the time of gravure ink printing.

<Base material>
Examples of the substrate that can be used in the printed material of the present invention include polyolefin resins such as polyethylene and polypropylene; polyester resins such as polyethylene terephthalate and polylactic acid; polycarbonate resins; polystyrene resins such as polystyrene, AS resin, and ABS resin; Polyamide resin; polyvinyl chloride, polyvinylidene chloride; cellophane; paper; aluminum; and film-like base materials made of these composite materials. Moreover, the vapor deposition base material which vapor-deposited inorganic compounds, such as a silica, an alumina, and aluminum, on plastic films, such as a polyethylene terephthalate and nylon, can also be used. A surface treatment such as a coating treatment such as polyvinyl alcohol or a corona treatment may be applied to the vapor deposition surface of the inorganic compound or the like.

<Laminate>
The laminated body of this invention has an adhesive layer and a film layer in order on the printing layer of the said printed matter. The laminate of the present invention is, for example, an extrusion laminating method in which a molten polyethylene resin and a film are laminated in this order on a printed layer via various anchor coating agents such as imine, isocyanate, polybutadiene, and titanium. (Also called extrusion lamination method); Applying urethane adhesive on the printing surface and laminating plastic film on it, dry lamination method or non-solvent lamination method; It can be obtained by a known laminating process such as a direct laminating method.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. “Part” and “%” in this section represent “part by mass” and “% by mass” unless otherwise specified.

(Hydroxyl value)
The hydroxyl value is a value obtained by converting the amount of hydroxyl group in 1 g of resin calculated by esterifying or acetylating the hydroxyl group in the resin with an excess of anhydrous acid and back titrating the remaining acid with alkali to the number of mg of potassium hydroxide. It is. It was measured according to JISK 0070 (1992).

(Amine value, acid value)
The amine value is the number of mg of potassium hydroxide equivalent to the equivalent amount of hydrochloric acid necessary for neutralizing the amino group contained in 1 g of the resin. The acid value is the number of mg of potassium hydroxide necessary to neutralize the acid groups contained in 1 g of resin.
The acid value was measured according to JISK 0070 (1992).
The amine value was measured according to JISK0070 (1992) by the following method.
-Measuring method of amine value 0.5-2g of sample is precisely weighed (sample amount: Sg). 30 mL of neutral ethanol (BDG neutral) is added to the accurately weighed sample and dissolved. The obtained solution is titrated with a 0.2 mol / L ethanolic hydrochloric acid solution (titer: f). The end point is the point at which the color of the solution has changed from green to yellow. Using the titration amount (AmL) at this time, the amine value is obtained by the following (Formula 2).
(Formula 2) Amine number = (A × f × 0.2 × 56.108) / S

(Weight average molecular weight)
The weight average molecular weight was determined by GPC (gel permeation chromatography) method. The molecular weight distribution was measured using “ShodexGPCSystem-21” manufactured by Showa Denko KK, and the molecular weight in terms of polystyrene was determined.

(Synthesis example 1) [Polyurethane resin PU1]
160 parts of a polyester polyol (hereinafter “PMPA”) having a number average molecular weight of 2000 obtained from adipic acid and 3-methyl-1,5-pentanediol, 20 parts of polypropylene glycol (hereinafter “PPG”) having a number average molecular weight of 2000, average A terminal isocyanate prepolymer solution was obtained by reacting 20 parts of polypropylene glycol having a molecular weight of 1000, 53.8 parts of isophorone diisocyanate (hereinafter “IPDI”), and 63.4 parts of ethyl acetate in a nitrogen stream at 80 ° C. for 4 hours. . Next, 23.1 parts of isophorone diamine (hereinafter “IPDA”), 2.0 parts of iminobispropylamine (hereinafter “IBPA”), 1.0 part of 2-ethanolamine (hereinafter “2EtAm”), ethyl acetate / isopropanol (hereinafter referred to as “below”) The obtained terminal isocyanate prepolymer solution was gradually added at 40 ° C. to a mixture of 589.7 parts of a mixed solvent of “IPA” = 50/50, and then reacted at 80 ° C. for 1 hour. Thus, a polyurethane resin solution PU1 having a solid content of 30%, an amine value of 11.1 mgKOH / g, a hydroxyl value of 3.3 mgKOH / g, and a weight average molecular weight of 35,000 was obtained.
Table 1 shows main synthesis conditions and properties of the obtained polyurethane resin solution.

(Synthesis example 2) [Polyurethane resin PU2]
A polyurethane resin solution PU2 was obtained in the same manner as in Synthesis Example 1 except that the raw materials shown in Table 1 were used. In Table 1, PPA, PEG, and TDI each represent the following compound.
PPA: polyester polyol which is a condensate of adipic acid and propylene glycol (1,2-propanediol),
PEG: polyethylene glycol,
TDI: Tolylene diisocyanate (methyl-1,3-phenylene diisocyanate).

(Synthesis Example 3) [Vinyl chloride-acrylic copolymer resin]
A solution obtained by dissolving 1.0 g of potassium peroxodisulfate (K ₂ S ₂ O ₈ ) in 500 g of ion-exchanged water was placed in a 1.0 L autoclave and deaerated. After the temperature was raised to 60 ° C., 425 g of a mixture consisting of 357 g of vinyl chloride, 63 g of 2-hydroxypropyl acrylate, and 5.0 g of sodium di-2-ethylhexylsulfosuccinate (product name: Aerosol OT) was added. The reaction was performed at 6.5 atmospheres. The polymerization reaction was continued until the autoclave pressure reached 2.5 atm. The produced emulsion was precipitated using sodium chloride, filtered, washed and dried to obtain a vinyl chloride-acrylic copolymer resin. Further, this vinyl chloride-acrylic copolymer resin was dissolved in ethyl acetate to obtain a varnish (PVAc1) having a solid content of 30%. The obtained resin had a content of 2-hydroxypropyl acrylate units of 14.0%, a weight average molecular weight of 50000, and a glass transition temperature of 70 ° C.

(Synthesis example 4) [Polyurethane resin PU3]
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, 80 parts of neopentyl glycol adipate diol (hydroxyl value: 56.6 mgKOH / g), 20 parts of polyethylene glycol (hydroxyl value: 278 mgKOH) / G), and 29.68 parts of isophorone diisocyanate were charged and reacted at 90 ° C. for 10 hours under a nitrogen stream to obtain a urethane prepolymer having an isocyanate group content of 2.84% by mass. To this was added 69.8 parts of ethyl acetate to obtain a uniform solution of urethane prepolymer. Next, the urethane prepolymer solution was added to a mixture comprising 7.97 parts of isophoronediamine, 0.11 part of di-n-butylamine, 139.1 parts of ethyl acetate, and 112.5 parts of isopropyl alcohol, and the mixture was heated at 45 ° C. A polyurethane resin solution PU3 was obtained by stirring for 5 hours. The obtained polyurethane resin solution PU3 had a solid content of 30.4% by mass, an amine value of 9.5 mgKOH / g, and a weight average molecular weight of 44,000.

(Example 1) [Preparation of gravure ink S1 for laminating]
40.0 parts of polyurethane resin solution PU1 (solid content 30%), vinyl chloride-vinyl acetate copolymer (Solvain TAO, manufactured by Nissin Chemical Industry Co., Ltd., vinyl chloride: vinyl acetate: vinyl alcohol (mass ratio) = 91: 2: 7, 30% solids ethyl acetate solution) 5.0 parts, silica silica particles 1 shown in Table 2 0.5 parts, C.I. I. 10.0 parts of Pigment Blue 15: 3 and 39.5 parts of a solution of N propyl acetate / IPA = 50/50 were mixed and dispersed with an Eiger mill for 30 minutes to obtain a gravure ink S1 for laminating. The formulation composition is shown in Table 4-1.

(Examples 2 to 23) [Preparation of gravure inks S2 to S23 for laminating]
Except for using the silica particles shown in Table 2, the glycol ether solvent shown in Table 3, and the raw materials shown in Tables 4-1 and 4-2, the gravure inks S2 to S23 for laminating were prepared in the same manner as in Example 1. Obtained. Abbreviations in Table 4-1 and Table 4-2 represent the following materials.
Solvain TAO: manufactured by Nissin Chemical Industry Co., Ltd., hydroxyl group-containing vinyl chloride-vinyl acetate copolymer, vinyl chloride: vinyl acetate: vinyl alcohol (mass ratio) = 91: 2: 7, solid content 30% ethyl acetate solution,
CAB38120BP: manufactured by Eastman Chemical Co., cellulose acetate butyrate, IPA solution having a solid content of 30%.

In Table 2, the average particle diameter is the average particle diameter of D50 by Coulter counter method, and the specific surface area is the value by BET method. In Table 3, the surface tension represents the static surface tension measured by the du Nouy method (ring method, ring method). In addition, it was judged that a solvent mixed with glycol ether solvent / water (mass ratio) = 50: 50 was water-soluble, and a solvent that separated layers was water-insoluble.

(Comparative Examples 1 to 13) [Preparation of gravure inks T1 to T13]
Gravure inks T1 to T13 were obtained in the same manner as in Example 1 except that the raw materials shown in Table 5 were used.

(Example 24) [Production of printed matter and laminate]
Each of the gravure inks S1 (blue ink) and S18 (red ink) obtained in the above examples was mixed solvent (methyl ethyl ketone “MEK”: N propyl acetate “NPAC”: isopropanol “IPA” (mass ratio) = 40. : 40:20), and diluted so that the viscosity was 16 seconds (25 ° C., Zahn Cup No. 3). Using the two types of diluted inks obtained, on the corona discharge-treated surface of a 12 μm thick corona discharge-treated polyester (PET) film (E-5100 manufactured by Toyobo Co., Ltd.) at a printing speed of 100 m / min in the order of indigo and red. Overprinting was performed to obtain a printed matter G1. For printing the diluted ink of S1, a Helio 175 line plate (plate type compressed plate with 75% solid pattern and 100% to 3% gradation pattern) was used. For printing the diluted ink of S17, a Helio 175 line plate (plate type Eron gate, plate with 75% solid pattern and 100% to 3% gradation pattern) was used. Printing was performed at a printing distance of 4000 m under conditions of a temperature of 25 ° C. and a humidity of 60%. After printing, the plate was idled for 60 minutes to evaluate the plate fog.

Each of the two printed materials G1 obtained as described above was coated with an ethyl acetate solution of polyether urethane laminate adhesive (TM320 / CAT13B manufactured by Toyo Morton Co., Ltd.) having different concentrations, and dried. For one printed matter G1, the solid content concentration of the adhesive solution was 25%, and the coating amount after drying was 1.5 g / m ² . For the other printed matter G1, the solid content concentration of the adhesive solution was 10%, and the coating amount after drying was 1.0 g / m ² . Each of these printed materials G1 is laminated by dry laminating with aluminum-deposited unstretched polypropylene (VMCP 2203, film thickness 25 μm, manufactured by Toray Film Processing Co., Ltd.), and two types of laminates with different adhesive coating amounts ( A dry laminate was obtained.
The following evaluation was performed about two types of laminated bodies from which the obtained gravure ink for lamination, printed matter, and the coating amount of an adhesive agent differed. The evaluation results are shown in Table 6-1. The laminate was evaluated after the laminate was held at 50 ° C. for 48 hours.

(Examples 24 to 45)
Printed materials G2 to G22 and laminates (dry laminates) were obtained and evaluated in the same manner as in Example 24 except that the ink combinations shown in Table 6-1 were used. The evaluation results are shown in Table 6-1.

(Comparative Examples 14 to 29)
Prints H1 to H16 and laminates (dry laminates) were obtained and evaluated in the same manner as in Example 24 except that the ink combinations shown in Table 6-2 were used. The evaluation results are shown in Table 6-2.

(Evaluation items and evaluation methods)
<Base material transferability>
The obtained printed materials G1 to G22 (Examples) and H1 to H16 (Comparative Examples) were evaluated for substrate transferability. Evaluation was made by the ratio (%) of the transferred area of the ink at the 5% gradation. The transferability was evaluated with indigo ink. The judgment criteria were as follows.
5: The ink transfer area ratio is 100%.
4. The ink transfer area ratio is 80% or more and less than 100%.
3. The ink transfer area ratio is 60% or more and less than 80%.
2. The ink transfer area ratio is 30% to less than 60%.
1 ... Ink transfer area ratio is less than 30%.
In addition, 5 and 4 are ranges in which there is no practical problem.

<Plate castability>
For plate gravure inks S1 to S23 (Examples) and T1 to T13 (Comparative Examples), evaluation of plate fogging was performed. The evaluation was performed based on the coloring area ratio on the plate after 60 minutes of idling. The judgment criteria were as follows.
5. The plate cover area ratio is 0% to less than 5%.
4. The plate covering area ratio is 5% to less than 10%.
3. The plate cover area ratio is 10% to less than 30%.
2. The plate cover area ratio is 30% to less than 50%.
1... Plate cover area ratio is 50% or more.
In addition, 5 and 4 are ranges in which there is no practical problem.

<Trapability>
For the obtained printed materials G1 to G22 (Example) and H1 to H16 (Comparative Example), the solid pattern overprinting portion and the gradation overprinting portion were evaluated for trapping properties using a KEYENCE microscope (VHX-5000). Went. The judgment criteria were as follows.
[Evaluation of solid pattern overprinted part]
5. There is no unevenness in the printing part.
4 ... Slightly uneven at the end of the printing part.
3 ··· There is a slight unevenness in the center of the printing section.
2 ... There is a large unevenness in the whole printing section.
1 ··· There is a large unevenness in the whole printing part, and the stripe pattern is clearly visible.
In addition, 5 and 4 are ranges in which there is no practical problem.
[Evaluation of gradation overprint]
5 ... Printing unevenness occurs when the plate depth is less than 70%.
4. Printing unevenness occurs when the plate depth is 70% to less than 80%.
3. Printing unevenness occurs when the plate depth is 80% or more and less than 90%.
2. Printing unevenness occurs when the plate depth is 90% to less than 100%.
1 ... All the red inks in the stack are halftone dots and do not spread at all.
In addition, 5 and 4 are ranges in which there is no practical problem.

<Laminate appearance>
The obtained printed laminates G1 to G22 (Examples) and H1 to H16 (Comparative Examples) were visually observed from the film surface to evaluate the appearance. The judgment criteria were as follows.
5. No delamination or unevenness in the printed part of the laminate (less than 1%).
4 ... Slight delamination and unevenness in the printed area of the laminate with an area ratio of 1% to less than 3%.
3. Delamination and unevenness are present at an area ratio of 3% to less than 20% in the printed portion of the laminate.
2. Delamination and unevenness are present at an area ratio of 20% to less than 50% in the printed part of the laminate.
1... Delamination and unevenness as a whole in the printed area of the laminate with an area ratio of 50% or more.
In addition, 5 and 4 are ranges in which there is no practical problem.

From the evaluation results shown in the table, it was found that the gravure ink for laminating of the present invention was excellent in printing transferability, plate fogging, and trapping property in overprinting, and further in the appearance after lamination.

This application claims priority based on Japanese Patent Application No. 2016-139452 filed on July 14, 2016, the entire disclosure of which is incorporated herein.

Claims (8)

1. A laminate gravure ink comprising an organic pigment (A), a binder resin (B), silica particles (C), and an organic solvent (D), wherein the laminate satisfies the following (1) and (2) Gravure ink.
   (1) The silica particles (C) are contained in an amount of 0.1 to 3% by mass in 100% by mass of the ink.
   (2) 0.1 to 20% by mass of the glycol ether organic solvent (d1) is contained in 100% by mass of the organic solvent (D).
2. 2. The gravure ink for lamination according to claim 1, wherein the silica particles (C) have an average particle diameter of 1 to 5 μm.
3. The gravure ink for laminating according to claim 1 or 2, wherein the glycol ether organic solvent (d1) has a surface tension of 22.0 to 30.0 mN / m.
4. The gravure ink for laminating according to any one of claims 1 to 3, wherein the binder resin (B) contains a polyurethane resin (b1).
5. Binder resin (B)
   Polyurethane resin (b1);
   And at least one resin selected from the group consisting of vinyl chloride-vinyl acetate copolymer resin (b2), vinyl chloride-acrylic copolymer resin (b3) and cellulose resin (b4),
   The gravure ink for lamination according to claim 4, wherein the resin (b1) to (b4) is contained in a total of 80 to 100% by mass in 100% by mass of the binder resin.
6. The binder resin (B) contains a total of 80 to 100% by mass of the polyurethane resin (b1) and the vinyl chloride-vinyl acetate copolymer resin (b2) in 100% by mass of the binder resin (B), and the resins (b1) and ( 6. The gravure ink for laminating according to 5, wherein the solid content mass ratio with respect to b2) is (b1) / (b2) = 95/5 to 40/60.
7. A printed matter having a printed layer made of the gravure ink for laminating according to any one of claims 1 to 6 on a substrate.
8. A laminate having at least an adhesive layer and a film layer in order on the print layer of the printed matter according to claim 7.